U.S. patent number 4,753,659 [Application Number 06/894,750] was granted by the patent office on 1988-06-28 for derivatives of cassia tora polysaccarides and their use.
This patent grant is currently assigned to Diamalt Aktiengesellschaft. Invention is credited to Friedrich Bayerlein, Ulrich Beck, Nikolaos Keramaris, Nikolaus Kottmair, Manfred Kuhn, Michel Maton.
United States Patent |
4,753,659 |
Bayerlein , et al. |
June 28, 1988 |
Derivatives of cassia tora polysaccarides and their use
Abstract
The invention relates to new alkyl ethers and phosphoric acid
esters of Cassia tora polygalactomannans and their use, alone or in
combination with other thickening agents, as thickening agents.
Inventors: |
Bayerlein; Friedrich
(Krailling, DE), Keramaris; Nikolaos (Eichenau,
DE), Kuhn; Manfred (Munich, DE), Beck;
Ulrich (Munich, DE), Kottmair; Nikolaus (Gauting,
DE), Maton; Michel (Gaucresson, FR) |
Assignee: |
Diamalt Aktiengesellschaft
(DE)
|
Family
ID: |
25816897 |
Appl.
No.: |
06/894,750 |
Filed: |
August 11, 1986 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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687059 |
Dec 28, 1984 |
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Foreign Application Priority Data
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Dec 29, 1983 [DE] |
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3347469 |
Aug 28, 1984 [DE] |
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3431589 |
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Current U.S.
Class: |
8/561; 514/23;
536/114; 514/54; 252/8.81; 252/8.83 |
Current CPC
Class: |
C08L
5/14 (20130101); C08B 37/0093 (20130101); C08B
37/0096 (20130101); C08B 37/0087 (20130101); C08L
5/14 (20130101); C08L 5/00 (20130101) |
Current International
Class: |
C08B
37/00 (20060101); C08B 37/14 (20060101); C08L
5/00 (20060101); C08L 5/14 (20060101); C09B
067/00 (); C07H 015/04 () |
Field of
Search: |
;514/23,54 ;536/114
;8/561 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Varshney et al., J. Arg. Food Chem., 21, 222, (1973)..
|
Primary Examiner: Brown; J. R.
Assistant Examiner: Peselev; Elli
Attorney, Agent or Firm: Robbins & Laramie
Parent Case Text
This application is a continuation of application Ser. No. 687,059,
filed Dec. 28, 1984, now abandoned.
Claims
What is claimed is:
1. An ester or ether derivative of Cassia tora polygalactomannans
selected from the group consisting of phosphoric acid esters and
substituted C.sub.1-4 -alkyl ethers, wherein said substituents are
selected from the group consisting of hydroxy, carboxy,
di-C.sub.1-4 -alkylammonium, tri-C.sub.1-4 -alkylammonium and
mixtures thereof.
2. The derivative of claim 1 wherein said ether is hydroxypropyl
ether.
3. The substituted C.sub.1-4 alkylether derivative of claim 1
wherein the degree of substitution is 0.03-3.0.
4. The derivative of claim 3 wherein the degree of substitution is
0.1-0.5.
5. The derivative of claim 1 having a viscosity of 100-40,000
mPas.
6. The derivative of claim 1 which has been depolymerized.
7. In a method of textile manufacture comprising the use of a
textile auxiliary, the improvement comprising using the derivative
of claim 1 as said textile auxiliary.
8. A method for thickening a solution comprising adding an
effective amount of the derivative of claim 1 to the solution as a
thickening agent.
9. The method of claim 8, wherein said solution is selected from
the group consisting of a printing paste for textile printing and a
dye solution for the continuous dyeing of textile substrates.
10. In the method of claim 7, wherein said textile auxiliary
further comprises a polysaccharide derivative selected from the
group consisting of xanthan, carrageenan, polymers of acrylic acid
or salts thereof, copolymers of acrylic acid or salts thereof and
mixtures thereof.
11. The method of claim 8, wherein an effective amount of a
polysaccharide derivative selected from the group consisting of
xanthan, carrageenan, polymers of acrylic acid or salts thereof,
copolymers of acrylic acid or salts thereof and mixtures thereof is
further added to the solution as a thickening agent.
12. The method of claim 9, wherein an effective amount of a
polysaccharide derivative selected from the group consisting of
xanthan, carrageenan, polymers of acrylic acid or salts thereof,
copolymers of acrylic acid or salts thereof and mixtures thereof is
further added to said solution as a thickening agent.
Description
The term "polygalactomannans" (or "galactomannans") is understood
to mean all polysaccharides which contain mannose and galactose
units and in addition can also contain minor amounts of other sugar
residues.
Polygalactomannans are mainly found in the endosperm portions of
seeds of various Leguminosae such as guar, locust bean, Cassia
occidentalis, tara, flame tree and the like. Both the pure
polygalactomannans mentioned above, and also many of their
derivatives, are known. Carboxyalkyl ethers and polyhydroxyalkyl
ethers of such polygalactomannans, derived from guar gum, locust
bean gum, honey locust, flame tree and the like, are described in
U.S. Pat. Nos. 2,477,544 and 2,496,670.
U.S. Pat. No. 3,467,647 describes polysaccharides which contain
both cationic and anionic substituents. Starches, locust bean gum
and guar are mentioned as polysaccharides, and phosphate esters,
among others, are mentioned as anionic substituents.
U.S. Pat. No. 4,031,306 describes the production of
polygalactomannan alkyl ethers. In U.S. Pat. No. 4,169,945 there is
described a process for the production of polygalactomannan alkyl
ethers, were the polygalactomannan can be guar or locust bean
gum.
U.S. Pat. No. 4,162,925 describes phosphate esters of locust bean
gum with a degree of substitution of 0.03-0.5. European Pat. No.
0,030,443 describes the phosphating of guar with a degree of
substitution of 0.1-0.5 and a viscosity of 50-4,000
milli-Pascal-seconds for a 2% aqueous solution, and also the use of
the guar phosphate ester in the paper industry.
It has now been found that the substituted and unsubstituted alkyl
ethers and the phosphate esters of polysaccharides which are
present in the endosperm portions of Cassia tora are, surprisingly,
distinguished by properties deviating from those of the
corresponding derivatives of polysaccharides from other sources.
They can, for example, advantageously be used as thickening agents
having improved stability to heat, acid, and shear. Such thickening
agents are used, e.g., in the paper industry as bulk additives, in
well drilling fluids as viscosity-increasing additives, and also in
printing pastes for textile printing.
Cassia tora (L. Baker), also termed Cassia obtusifolia (Linn),
represents a kind of cassia which thrives preferably in a tropical
climate. The polysaccharides wich are present in the endosperm
portions of Cassia tora are built up chiefly of galactose and
mannose units, and only a minor amount of other sugar residues. In
particular, they are polygalactomannans.
The pure galactomannans of various botanical origins show slight
differences, as regards their chemical structure and composition,
which exert an influence on cold water solubility, thickening
properties, and interactions with other polysaccharides
(carrageenan, xanthan). The best known polygalactomannans are those
from Cyamopsis tetragonoloba L. (guar), Cesalpinia spinosa L.
(tara), and Ceratonia siliqua L. (locust bean). Their molecular
weights are about 200,000-300,000. The main chain is composed of
mannose molecules joined by beta-1,4-glucosidic bonds.
Unsubstituted polymannans are completely insoluble in water. The
attachment of galactose units to the primary hydroxyl groups of the
mannose units (C-6 atom of the mannose molecule) by
alpha-1,6-glucosidic bonds increases water solubility, particularly
cold water solubility.
The greater the substitution of the mannose main chain with
galactose molecules, the greater is also the cold water solubility
of the polygalactomannan.
Locust bean gum (abbreviated as LBG), which has hitherto been
preferably used as the raw material for the products for textile
finishing, is obtained from the locust bean trees. Locust bean
trees principally flourish in the Mediterranean, California, and
Australia, and give a full harvest only after 10-15 years of
growth. Hence, LBG is only available to the user to a limited
degree. This has resulted in a search for an alternative.
The alkyl ethers according to the invention are in general those
having 1-4 carbon atoms in the alkyl group, and especially methyl
ethers, ethyl ethers, n-propyl ethers, isopropyl ethers as well as
butyl ethers and the structural isomers of the butyl ethers of the
polysaccharides present in the endosperm of Cassia tora. They can
be produced by reacting Cassia tora galactomannan with an alkyl
halide or diazomethane in a known manner.
Thus, the reaction of the polygalactomannans derived from the
endosperm portions of Cassia tora with methyl halides gives methyl
ethers, and with ethyl halide gives ethyl ethers. Preferred methyl
and ethyl halides are methyl and ethyl chlorides.
It is preferred that the substituted alkyl ethers according to the
invention possess 1-4 carbon atoms in the alkyl group and bear as
substituents hydroxyl, carboxyl, and trialkylammonium groups.
Examples of the compounds according to the invention are
hydroxypropyl cassia galactomannan, hydroxyethyl cassia
galactomannan, and carboxymethyl cassia galactomannan. A
particularly preferred ether is the hydroxypropyl ether.
These compounds according to the invention can be produced by
reacting Cassia tora galactomannans in a known manner with alkylene
oxides, acrylonitrile, halogen fatty acid derivatives, or
quaternary ammonium compounds containing an epoxyalkyl or
halohydrin group.
Thus the reaction of the polygalactomannans derived from the
endosperm portions of Cassia tora with alkylene oxides gives
hydroxyalkyl ethers. Preferred alkylene oxides are ethylene oxide
and propylene oxide. Nonionic compounds are produced in these
reactions.
The reaction of Cassia tora galactomannans with quaternary ammonium
compounds which contain an epoxyalkyl or halohydrin group gives
cationic derivatives. Preferred quaternary compounds are
glycidyl-trialkylammonium halides or
3-halogen-2-hydroxypropyl-trialkylammonium halides. The
particularly preferred hydroxyalkyl ethers substituted with di- or
tri-alkylammonium are the di- and tri-methylammonium-hydroxyalkyl
ethers. The reaction of Cassia tora galactomannans with halogen
fatty acids or their salts and with acrylic acid derivatives leads
to anionically substituted alkyl galactomannans. The preferred
anionic derivative is carboxymethyl galactomannan, which can be
produced by reacting Cassia tora galactomannan with the sodium salt
of monochloroacetic acid.
The phosphated Cassia tora galactomannan according to the invention
is the ester of phosphoric acid and the polygalactomannans derived
from the endosperm portions of Cassia tora. Phosphoric acid, and/or
its alkali or ammonium salt, is used for the esterification of the
polygalactomannan. By all indications, the resulting ester is the
monoester of phosphoric acid.
The phosphating reaction can be carried out in many ways. The
Cassia tora polygalactomannan can be first mixed with an aqueous
solution of the alkali hydroxide and then with the phosphoric acid.
The Cassia tora polygalactomannan can also be first mixed with the
phosphoric acid and then with an aqueous solution of the alkali
hydroxide. The alkali salt of phosphoric acid can also be first
produced from the phosphoric acid and the alkali hydroxide, and
then mixed with Cassia tora polygalactomannan. A mixture can first
be produced from monodosium phosphate and disoium phosphate in a
1:1 molar ratio and then the aqueous solution of it, with a pH of
about 6, can be mixed with Cassia tora polygalactomannan. Cassia
tora polygalactomannan can be used in the form of powder or chips.
The phosphating reaction is carried out at 115.degree.-175.degree.
C., preferably at about 150.degree. C., for 30 minutes to 5
hours.
When sodium hydroxide and phosphoric acid are mixed in succession
with the Cassia tora polygalactomannan, 10-65 parts by weight of
sodium hydroxide, 15-100 parts by weight of phosphoric acid and
50-300 parts by weight of water are mixed for the reaction of 162
parts by weight of polygalactomannan, in a proper portion such that
the pH value lies between 6 and 7. The reagents are preferably used
in a proportion of 27.5 parts by weight of sodium hydroxide to 45.5
parts by weight of phosphoric acid as well as 200 parts by weight
of water for the reaction of 162 parts by weight of Cassia tora
polygalactomannan.
The degree of substitution of the ethers and esters, especially the
alkyl ethers, according to the invention is between 0.03 and about
3.0, preferably between 0.1 and 0.5; the viscosity (3 weight
percent in water) is about 100-40,000 mPas (Brookfield RVT, at 20
rpm and 20.degree. C.). For the phosphoric acid esters according to
the invention, a degree of substitution of 0.03-1.5, in particular
of 0.1-0.5, and a viscosity of 100-10,000 mPas are preferred.
The galactomannan derivatives according to the invention can also
be used in a depolymerized form as thickening agents. The molecular
weights and viscosities can be reduced by hydrolytic or oxidative
depolymerization.
It is known to thicken dyestuff solutions or dispersions for the
printing and dyeing of textile substrates by means of natural
polysaccharides or their derivatives. Such natural polysaccharides,
or derivatives thereof, used in textile finishing are obtained
from, e.g., starches, alginates, transparent gums or plant gums and
galactomannans. Unmodified galactomannans are both cold water
soluble--e.g., the guar gums--and also insoluble, or only partially
soluble, in cold water--e.g., locust bean gum. Cold water
solubility, or improved cold water solubility, can be achieved by
chemical derivatization or, in some cases, by mechanical or thermal
decomposition.
According to U.S. Pat. No. 2,477,544, locust bean gum and locust
bean gum ethers, abbreviated below as LBG and LBG ethers, are
especially recommended from the series of galactomannans for the
thickening of aqueous dyeing systems.
The advantage of LBG and LBG ethers is an excellent penetration of
the printing pastes, a very good leveling ability, brilliant dye
appearance, very good film formation, and good rinsability from the
textile substrate. Apart from this, the processability of the
printing pastes on the machine is positively influenced by the use
of LBG or LBG ethers. This is especially clearly evidenced in
easier transferability of the printing pastes from the depressions
of the gravure roller onto the substrate and a low sensitivity to
squeezing. These good properties are not achieved, or only
partially achieved, by the other galactomannans or their
derivatives as hitherto used in textile finishing.
It has now surprisingly been found that the present invention's
alkyl ethers and phosphate esters of the polygalactomannans present
in the endosperm portions of Cassia tora have, and even surpass,
the described advantages of LBG or LBG ethers, but do not possess
their disadvantages.
They are outstandingly suitable as thickening agents in general,
and in particular as printing thickening agents for textile and
paper printing.
Unmodified galactomannans are both cold water soluble--e.g., guar
gum--and also insoluble, or only partially soluble, in cold
water--e.g., locust bean gum. Cold water solubility, or improved
cold water solubility, can be achieved by chemical derivatization
or, in some cases, by mechanical or thermal decomposition. While
Cassia tora polygalactomannan is only slightly soluble in cold and
hot water, the alkyl ethers and the phosphate esters have good
solubility in cold and hot water.
Apart from this, they can be utilized as well drilling fluid
auxiliaries, in mining, and also in the explosives industry.
Since the Cassia alkyl ethers according to the invention are
thermally stable, they can be utilized, in particular, in petroleum
recovery and well drilling. The viscosity of the Cassia derivatives
according to the invention remains stable for several hours on
keeping in closed autoclaves, both in the neutral and in the
strongly alkaline region, and at a temperature above 120.degree.
C.
The derivatives according to the invention of the galactomannans
derived from the endosperm of Cassia tora can be used alone,
partially in combination with each other, or together with other
polysaccharide derivatives. Such other polysaccharide derivatives
are, e.g., guar gum, depolymerized guar gum, carboxymethyl starch,
British gum, sodium alginate, xanthan gum, and carboxymethyl
guar.
Examples of suitable combinations are:
______________________________________ (1) 1-100 parts by weight
methyl cassia or hydroxymethyl cassia 99-0 parts by weight guar gum
(2) 1-100 parts by weight methyl cassia 99-0 parts by weight
carboxymethyl starch (3) 20-60 parts by weight methyl cassia 10-30
parts by weight sodium alginate 70-10 parts by weight carboxymethyl
starch (4) 10-60 parts by weight methyl cassia 10-30 parts by
weight hydroxypropyl cassia 80-20 parts by weight carboxymethyl
guar (5) 20-60 parts by weight ethyl cassia 10-30 parts by weight
methyl cassia 70-10 parts by weight carboxymethyl starch (6) 20-60
parts by weight allyl cassia 10-30 parts by weight hydroxypropyl
cassia 70-10 parts by weight carboxymethyl starch (7) 5-100 parts
by weight hydroxyethyl cassia 95-0 parts by weight depolymerized
guar gum (8) 20-80 parts by weight hydroxypropyl cassia 80-20 parts
by weight carboxymethyl starch (9) 20-60 parts by weight
hydroxyethyl cassia 10-30 parts by weight sodium alginate 70-10
parts by weight carboxymethyl starch (10) 30-100 parts by weight
hydroxypropyl cassia 70-0 parts by weight of xanthan gum (11) 10-60
parts by weight trimethylammonium-hydroxypropyl cassia chloride
90-40 parts by weight British gum (12) 10-60 parts by weight
carboxymethyl cassia 10-30 parts by weight carboxymethyl guar 80-20
parts by weight carboxymethyl starch
______________________________________
Examples of suitable thermally stable combinations are:
______________________________________ (1) 5-100 parts by weight
methyl cassia 95-0 parts by weight methyl guar (2) 20-60 parts by
weight methyl cassia 10-30 parts by weight methyl guar 70-10 parts
by weight allyl cassia (3) 20-60 parts by weight methyl cassia
10-30 parts by weight ethyl cassia 70-10 parts by weight methyl
guar ______________________________________
Cotton, rayon, wool, silk, acetate, triacetate, polyester,
polyamide and polyacrylonitrile can preferably be processed in the
utilization of the described Cassia tora derivatives in aqueous
textile printing and for the continuous dyeing of planar textile
structures of cellulosic, animal, and synthetic materials or their
mixtures.
In a further aspect of the present invention, it was found that the
alkyl ethers and phosphate esters of Cassia tora described above,
and also other derivatives of Cassia tora, exhibit a synergistic
effect with other materials which are suitable as thickening
agents, such as carrageenan, agar, xanthan, polyacrylates and
polymethacrylates, and in particular with xanthan.
Not all Cassia tora derivatives exhibit this synergistic effect:
for example, cationic derivatives are not suitable.
It was found that with increasing degree of substitution of the
Cassia tora ethers and esters, the water solubility of these
derivatives admittedly increases, but the synergism decreases.
Synergism is no longer present with total substitution.
Suitable Cassia tora derivatives which show this synergism are
alkyl ethers, carboxyalkyl ethers, hydroxyalkyl ethers, especially
those in which the alkyl group has 1-4 carbon atoms, and also the
said phosphate esters.
By "xanthan" is understood a high-molecular polysaccharide,
obtained in a fermentation process with the microorganisms
Xanthomonas mulracean, Xanthomonas campestris, Xanthomonas
phaseoli, Xanthomonas carotae, and the like (see U.S. Pat. Nos.
3,557,016 and 4,038,206).
Carrageenan is a galactan extracted from red algae (Rhodophyceae),
and partially contains anhydrogalactose and is partially esterified
with sulfuric acid.
U.S. Pat. No. 4,246,037 describes the synergistic viscosity
increase of mixtures of xanthan gum and tamarind meal (meal from
Tamarindus indica).
U.S. Pat. No. 3,557,016 discloses that an increase of viscosity
takes place when a mixture of locust bean gum (90-50%) and xanthan
(10-50%) is added to hot water (66.degree.-82.degree. C.) and is
allowed to stand at this temperature for more than 15 minutes. In
the U.S. Food Chemical Codex, II, p. 856, it is disclosed that this
cross-linkage (synergism) is used as evidence of locust bean
gum.
U.S. Pat. No. 4,162,925 describes the synergistic viscosity
increase of mixtures of xanthan gum and phosphate esters of locust
bean gum with a degree of substitution of 0.03-0.5.
It has now been found that both the cold water soluble Cassia tora
galactomannan ethers and the cold water soluble Cassia tora
galactomannan esters show synergistic behavior with xanthan gum,
carageenan, and other substances. When carrageenan is used as a
constituent, the viscosity increase due to synergism first takes
place after the mixture has been heated in water for at least 15
minutes.
When xanthan gum is used as the constituent, heating or boiling of
the aqueous mixture is no longer necessary.
The mixing ratio of Cassia tora galactomannan ether or ester to the
synergistic component such as, e.g., xanthan gum, can be varied
greatly. The synergistic mixtures according to the invention
consist of 10-90 weight percent Cassia tora galactomannan ether or
ester and correspondingly 90-10 supplementary parts of xanthan gum,
making up 100 percent. The maximum viscosity increase is achieved,
however, with mixtures of 75-50 parts by weight of Cassia tora
galactomannan ether or ester and correspondingly 25-50 parts by
weight of xanthan gum, making up 100 percent.
By simple brief stirring of the mixture into cold water (without
heating or strong shear forces), hydration takes place within 5
minutes. Complete hydration is reached after about 15 minutes.
The gels according to the invention are produced by briefly
stirring 0.3-2 weight percent of the mixture of Cassia tora
galactomannan ether or ester and xanthan with cold water. The
viscosity or the strength of the gel increases with increasing
concentration. Flowable gels are produced at a concentration of
0.3-0.7 percent (in water, based on dry material). At a
concentration above 1 percent, the gels are no longer flowable, but
are more or less solid. The mixtures of cassia galactomannan ether
or ester and xanthan can also contain other cold water soluble
thickening agents (such as guar and guar derivatives, LBG
derivatives, tara and tara derivatives, cellulose and starch
derivatives, and tamarind derivatives).
The gels according to the invention can be used in well drilling
and petroleum recovery. The viscosity of the gels according to the
invention remains stable on keeping for several days in closed
autoclaves both in the neutral and in the strongly alkaline region
and at a temperature above 120.degree. C. Apart from this, they can
be used in the textile, paper, and explosives industries. Quite
generally, these gels can also be utilized, due to their particular
suspending ability, wherever it is necessary to hold solid
particles in suspension in aqueous liquids and prevent them from
settling out.
The invention is illustrated in detail in the following examples.
The "parts" stated in the examples are parts by weight. The
viscosity, unless otherwise stated, was measured on a Brookfield
rotary viscometer RVT at 20.degree. C. and 20 rpm, with the
suitable spindle.
EXAMPLE 1
Hydroxypropyl cassia galactomannan
162 parts of polygalactomannan from Cassia tora were reacted with
58 parts of propylene oxide in an alkaline aqueous medium at a
temperature of 60.degree. C. A light brown solid, soluble in cold
water, was obtained.
The viscosity (3% in water, measured on the Brookfield rotary
viscometer RVT, spindle 6, 20.degree. C. and 20 rpm) was about
20,000 mPas. The average molecular weight was about 200,000 and the
degree of substitution was 0.65.
EXAMPLE 2
Hydroxyethyl cassia galactomannan
162 parts of polygalactomannan from Cassia tora were reacted with
22 parts of ethylene oxide in an alkaline aqueous medium at a
temperature of 42.degree. C. A light brown solid, soluble in cold
water, was obtained.
The viscosity (3% in water, measured on a Brookfield rotary
viscometer RVT, spindle 6, 20.degree. C. and 20 rpm) was about
40,000 mPas. The average molecular weight was about 250,000, and
the degree of substitution was 0.31.
EXAMPLE 3
Carboxymethyl cassia galactomannan
162 parts of polygalactomannan from Cassia tora were reacted with
35 parts of the sodium salt of monochloroacetic acid and 15 parts
of sodium hydroxide in aqueous medium at a temperature of
68.degree. C. A light brown solid, soluble in cold water, was
obtained.
The viscosity (3% in water, measured on a Brookfield rotary
viscometer RVT, spindle 6, 20.degree. C. and 20 rpm) was about
15,000 mPas. The average molecular weight was about 180,000, and
the degree of substitution was 0.23.
EXAMPLE 4
2-hydroxy-3-(trimethylammonium)propyl Cassia tora galactomannan
chloride
200 parts of polygalactomannan from Cassia tora were reacted with
68 parts of glycidyl-trimethylammonium chloride (75% aqueous
solution) in an alakline aqueous medium at a temperature of
52.degree. C. A light brown solid, soluble in cold water, was
obtained.
The viscosity (3% in water, measured on a Brookfield rotary
viscometer RVT, spindle 6, 20.degree. C. and 20 rpm) was 18,000
mPas. The average molecular weight was about 190,000, and the
degree of substitution was 0.18.
EXAMPLE 5
Hydroxypropyl cassia galactomannan, depolymerized
162 parts of polygalactomannan from Cassia tora were reacted with
25 parts of propylene oxide in an alkaline aqueous medium at a
temperature of 60.degree. C. After depolymerization with 20 parts
ofhydrogen peroxide, a light brown solid, soluble in cold water,
was obtained.
The viscosity (10% in water, measured on a Brookfield rotary
viscometer RVT, spindle 6, 20.degree. C. and 20 rpm) was about
10,000 mPas. The average molecular weight wasabout 18,000, and the
degree of substitution was 0.27.
EXAMPLE 6
200 parts of endosperms from Cassia tora were placed in a kneading
mixer and, with the mixer running, were treated with a solution of
34.07 parts of sodium hydroxide and 65.47 parts of phosphoric acid
(85%) in 240 parts of water. After kneading for 45 minutes at room
temperature, the reaction material was kneaded for 31/2 hours at
158.degree.-160.degree. C. After cooling and milling, a cold water
soluble product, which was strongly anionic, was obtained.
Precipitation took place with polyvalent cations (or cation-active
galactomannans). The degree of substitution DS(PO.sub.4.sup.3-) was
0.25.
______________________________________ Reaction time at
158.degree.-160.degree. C. Viscosity - mPas (3%)
______________________________________ 1 hour 600 11/2 hours 5,350
2 hours 3,900 21/2 hours 1,950 3 hours 380
______________________________________
For comparison, the following control experiment was performed: 200
parts of polysaccharide from endosperms of Cassia tora were placed
in a kneading mixer and, with the mixer running, treated with 250
parts of water. After kneading for 45 minutes at room temperature,
the strongly swollen chips were heated for 90 minutes at
158.degree.-160.degree. C. After milling, the brownish powder thus
prepared showed hardly any viscosity. Also, only slight hydration
took place after boiling. A 3% mixture showed no viscosity in the
cold, and a viscosity of 370 mPas after boiling.
EXAMPLE 7
400 parts of polysaccharide from endosperms of Cassia tora were
placed in a kneading mixer and, with the mixer running, were
treated with a solution of 68 parts of sodium hydroxide and 132
parts of phosphoric acid (85%) in 480 parts of water. The reaction
material was mixed for 2 hours at room temperature and a further 2
hours at 60.degree. C. It was then heated to
158.degree.-160.degree. C. and kneaded at this temperature for 3
hours. After milling, a brownish, cold water soluble product was
obtained with a degree of substitution of 0.2.
______________________________________ Reaction time at
158.degree.-160.degree. C. Viscosity - mPas (3%)
______________________________________ After 90 minutes 440 120
minutes 3,450 150 minutes 3,750 180 minutes 1,300
______________________________________
EXAMPLE 8
200 parts of polysaccharide from endosperms of Cassia tora were
placed in a kneading mixer and, with the mixer running, treated
with a solution of 33 parts of phosphoric acid (85%) in 100 parts
of water and mixed for 30 minutes at room temperature. A solution
of 17 parts of sodium hydroxide in 80 parts of water was then added
and mixed for a further 15 minutes.
The reaction material was kneaded for 3.5 hours at
158.degree.-160.degree. C. After milling, a cold water soluble
product was obtained.
______________________________________ Reaction time at
158.degree.-160.degree. C. Viscosity - mPas (3%)
______________________________________ After 30 minutes 210 60
minutes 570 90 minutes 2,000 120 minutes 2,750 150 minutes 3,400
180 minutes 1,850 210 minutes 830
______________________________________
EXAMPLE 9
200 parts of polysaccharide from endosperms of Cassia tora were
placed in a kneading mixer and, with the mixer running, treated
with a solution of 66 parts of phosphoric acid (85%) in 120 parts
of water and mixed for 30 minutes at room temperature. A solution
of 34 parts of sodium hydroxide in 120 parts of water was then
added and mixed for a further 30 minutes. The reaction material was
kneaded for 31/2 hours at 158.degree.-160.degree. C. After milling,
a cold water soluble product was obtained.
______________________________________ Reaction time at
158.degree.-160.degree. C. Viscosity - mPas (3%)
______________________________________ After 60 minutes 1,425 90
minutes 4,000 120 minutes 4,700 150 minutes 5,500 180 minutes 3,500
210 minutes 1,500 ______________________________________
EXAMPLE 10
200 parts of polysaccharide from endosperms of Cassia tora were
placed in a kneading mixer and, with the mixer running, were
treated with a solution of 34 parts of sodium hydroxide in 120
parts of water and mixed for 60 minutes. A solution of 66 parts of
phosphoric acid (85%) in 120 parts of water was then added and
mixed for a further 60 minutes at room temperature. The reaction
material was kneaded for 31/2 hours at 158.degree.-160.degree. C.
After milling, a cold water soluble product was obtained.
______________________________________ Reaction time at
158.degree.-160.degree. C. Viscosity - mPas (3%)
______________________________________ After 60 minutes 1,000 90
minutes 2,350 120 minutes 2,800 150 minutes 3,000 180 minutes 2,000
210 minutes 850 ______________________________________
EXAMPLE 11
200 parts of polysaccharides from endosperms of Cassia tora were
placed in a kneading mixer and, with the mixer running, treated
with a solution of 25.2 parts of monosodium phosphate and 29.8
parts of disodium phosphate in 260 parts of water and mixed for 30
minutes at room temperature. The reaction material was kneaded for
3 hours at 158.degree.-160.degree. C. After milling, a cold water
soluble product was obtained.
______________________________________ Reaction time at
158.degree.-160.degree. C. Viscosity - mPas (3%)
______________________________________ After 60 minutes 1,400 90
minutes 3,150 120 minutes 3,700 150 minutes 3,200 180 minutes 2,300
______________________________________
EXAMPLE 12
200 parts of polysaccharides from endosperms of Cassia tora were
placed in a kneading mixer, and, with the mixer running, treated
with a solution of 66 parts of phosphoric acid (85%) in 120 parts
of water and mixed for 30 minutes at room temperature. A solution
of 34 parts of sodium hydroxide in 120 parts of water was then
added and mixed for a further 30 minutes. The reaction material was
kneaded for 120 minutes at 158.degree.-160.degree. C. After
milling, a cold water soluble product was obtained with a viscosity
of 4,500 mPas (3%).
The brownish product was placed in an efficient mixer, treated with
a solution of 5 parts of sodium hydroxide and 15 parts of hydrogen
peroxide (32%) in 20 parts of water, and mixed for 15 minutes at
room temperature. After a depolymerization time of 120 minutes at
80.degree. C., neutralization with citric acid and drying in vacuum
were performed. The viscosity was now 180 mPas (3%).
EXAMPLE 13
162 parts of polysaccharide from endosperms of Cassia tora were
placed in a kneading mixer and, with the mixer running, treated
with a solution of 16.8 parts of sodium hydroxide in 162 parts of
water. After mixing for 60 minutes at room temperature, 20.2 parts
of methyl chloride were added, and the kneader was closed. The
reaction material was mixed for a further 4 hours at a reaction
temperature of 70.degree.-75.degree. C. The excess methyl chloride
was removed under vacuum and the product was dried and milled. The
product was cold and hot water soluble and the viscosity was 18,500
mPas, 3% (measured with Brookfield, Model RVT at 20 rpm and
20.degree. C.).
EXAMPLE 14
600 parts of 65% isopropanol were placed in a suitable stirrer
vessel with thermometer and reflux cooler and, with the mixer
running, 100 parts of meal from endosperms of Cassia tora and 20
parts of sodium hydroxide in 20 parts of water were added. After
mixing for 45 minutes at about 25.degree. C., 33 parts of methyl
iodide were added and the mixture was heated to 72.degree. C. The
reaction material was mixed for a further 5 hours at a temperature
of 73.degree.-75.degree. C. The product was then filtered off and
the filter cake was dried in a drying chamber. The powdery product
was cold and hot water soluble. The viscosity was:
(a) 6,500 mPas, 3% in conductivity water
(b) 3,800 mPas, 3% in 30% methanol
(measured in Brookfield, Model RVT at 20 rpm and 20.degree. C.)
EXAMPLE 15
Mixtures of Cassia tora galactomannan phosphate ester (=PhCaGa) and
xanthan gum
The percent viscosity increase brought about by synergism between
PhCaGa and xanthan is demonstrated in this example. Mixtures were
prepared of 10-90 weight percent of PhCaGa and, correspondingly,
90-10 parts (adding to 100 percent) of xanthan (Rhodigel 23).
Respectively, 3 parts of these mixtures were stirred into 297 parts
of water (cold, about 20.degree. C.) with a stirrer for about 5
minutes, and after 20 minutes the viscosity was measured on a
Brookfield rotary viscometer RVT at 20.degree. C. and 20 rpm with
the suitable spindle. Table I shows the proportions in which the
two components were mixed, the theoretically calculated (expected)
viscositiy, the actual (found) viscosity, and the percentage
increase in viscosity.
TABLE I ______________________________________ Synergism of Cassia
Tora galactomannan phosphate ester (PhCaGa)/xanthan gum mixtures
Mixture Theor. Visc. Actual Visc. % Xanthan PhCaGa (mPas) 1% (mPas)
1% Increase ______________________________________ 100 0 -- 3,060
-- 90 10 2,763 4,170 51% 70 30 2,169 7,000 222% 60 40 1,872 9,200
391% 50 50 1,575 10,000 535% 40 60 1,278 11,600 807% 30 70 981
10,250 945% 10 90 387 2,575 565% 0 100 -- 90 --
______________________________________
A mixture of 60 parts of Cassia tora galactomannan phosphate ester
and 40 parts of xanthan was prepared. A 0.5% solution of this
mixture in water at room temperature formed a gel, which had a gel
structure such that it prevented locust bean kernels from settling
out for more than 24 hours.
EXAMPLE 16
Mixtures of hydroxypropyl cassia galactomannan (=HPCaGa) and
xanthan
The percentage viscosity increase effected by synergism between
hydroxypropyl cassia galactomannan and xanthan (Rhodigel 23) is
demonstrated in this example. Mixtures of 75 or 50 weight percent
of hydroxypropyl cassia galactomannan and, correspondingly, 25 or
50 percent complementary proportions of xanthan were prepared.
Respectively 3 parts of these mixtures were stirred in 297 parts of
water (cold, about 20.degree. C.) with a stirrer for about 5
minutes, and after 20 minutes the viscosity was measured on the
Brookfield RVT at 20.degree. C. and 20 rpm with the suitable
spindle. Table II shows the viscosity increase.
TABLE II ______________________________________ Mixture Theor.
Visc. Actual Visc. % Xanthan HPCaGa (mPas) (mPas) Increase
______________________________________ 100 0 -- 3,000 -- 50 50
1,600 7,000 337 25 75 900 7,500 733 0 100 -- 200 --
______________________________________
EXAMPLE 17
Mixtures of hydroxyethyl cassia galactomannan (=HECaGa) and
xanthan
The percentage increase in viscosity effected by the synergism
between hydroxyethyl cassia galactomannan and xanthan (Rhodigel 23)
is demonstrated in this example. Mixtures of 75 or 50 weight
percent of hydroxyethyl cassia galactomannan and, correspondingly,
25 or 50 percent complementary proportions of xanthan were
prepared. Respectively 3 parts of these mixtures were stirred in
297 parts of water (cold, 20.degree. C.) with a stirrer for 5
minutes, and after 20 minutes the viscosity was measured on the
Brookfield RVT.
TABLE III ______________________________________ Mixture Theor.
Visc. Actual Visc. % Xanthan HECaGa (mPas) (mPas) Increase
______________________________________ 100 0 -- 3,000 -- 50 50
1,630 4,800 194 25 75 945 5,200 450 0 100 -- 260 --
______________________________________
EXAMPLE 18
Mixture of carboxymethyl cassia galactomannan (=CMCaGa) and
xanthan
Various mixtures of carboxymethyl cassia galactomannan with xanthan
were prepared and stirred in 1% amount into cold water.
TABLE IV ______________________________________ Mixture Theor.
Visc. Actual Visc. % Xanthan CMCaGa (mPas) (mPas) Increase
______________________________________ 100 0 -- 3,000 -- 50 50
1,545 8,500 450 25 75 817.5 8,000 878 0 100 -- 90 --
______________________________________
EXAMPLE 19
Mixture of methyl cassia galactomannan (=MCaGa) with xanthan
Various mixtures of methyl cassia galactomannan with xanthan were
prepared and stirred in a 1% amount into cold water.
TABLE V ______________________________________ Mixture Theor. Visc.
Actual Visc. % Xanthan MCaGa (mPas) (mPas) Increase
______________________________________ 100 0 -- 3,000 -- 50 50
1,650 7,000 324 25 75 975 6,200 538 0 100 -- 300 --
______________________________________
EXAMPLE 20
The thermal and alkali stability of the aqueous solution of the
mixture of 75 parts Cassia tora polygalactomannan derivative and 25
parts of xanthan gum are demonstrated in this example.
Respectively, 1.5 parts of these mixtures were stirred with a
stirrer for about 5 minutes at room temperature into 298.5 parts of
an artificial sea water consisting of 96.7 parts of conductivity
water, 3 parts of NaCl, 0.2 parts of MgCl.sub.2.H.sub.2 O, and 1
part of KCl. After 15 minutes, the viscosity was measured on the
Brookfield rotary viscometer at 20.degree. C. and 100 rpm, with
spindle 3.
The following table shows the viscosity of the respective mixture
at 20.degree. C. and a pH of 7 or 10.7.
______________________________________ Viscosity at 20.degree. C.
Mixture pH 7 pH 10.7 ______________________________________
HPCaGa/Xanthan (75:25) 150 mPas 145 mPas HECaGa/Xanthan (75:25) 200
mPas 200 mPas CMCaGa/Xanthan (75:25) 40 mPas 45 mPas MCaGa/Xanthan
(75:25) 120 mPas 125 mPas PHCaGa/Xanthan (75:25) 230 mPas 220 mPas
______________________________________
These solutions were kept for 16 hours in autoclave bottles in the
drying chamber at 115.degree. C., and the viscosity was then
measured at 20.degree. C. Before the measurement, the solutions
were stirred for 5 minutes in the high speed stirrer.
______________________________________ Mixture Viscosity at 20
.degree. C. Actual pH value ______________________________________
HPCaGa/Xanthan (75:25) 280 mPas 9.1 HECaGa/Xanthan (75:25) 270 mPas
9.6 CMCaGa/Xanthan (75:25) 320 mPas 9.6 MCaGa/Xanthan (75:25) 200
mPas 9.6 PHCaGa/Xanthan (75:25) 160 MPas 10.4
______________________________________
EXAMPLE 21
Mixtures of hydroxypropyl cassia galactomannan (=HPCaGa) with
various DS (degrees of substitution) and xanthan
In this example, the percentage viscosity reduction in 50%
methanol, due to synergism between hydroxypropyl cassia
galactomannan with a DS of 0.3 or 0.4 and xanthan (Rhodigel 23), is
described. Mixtures of 75 weight percent of HPCaGa and
corresponding 25% complementary proportions of xanthan were
prepared. Respectively, 3 parts of these mixtures in 297 parts of
50% methanol (cold, about 20.degree. C.) were stirred with a
stirrer for about 20 minutes, and after 20 minutes the viscosity
was measured on the Brookfield RVT at 20.degree. C. and 20 rpm with
the suitable spindle.
Table VI shows the viscosity increase.
TABLE VI ______________________________________ Viscosity in 50%
Methanol, mPas Xan- HPCaGa Actual Viscosity Theor. % In- than DS:
0.3 DS: 0.4 1% 5% 0.25% Viscosity crease
______________________________________ 100 pts. -- -- 3000 -- --
100 pts. -- -- -- 800 -- 100 pts. -- -- -- -- 200 -- 100 pts. -- 55
-- -- -- -- 100 pts. 110 -- -- 25 pts. 75 pts. -- 2500 -- -- 241
938 25 pts. -- 75 pts. 2000 -- -- 282 609
______________________________________
The gel structure of these gels remains stable, even after 3 days
at -20.degree. C., and prevents the settling out of, e.g., locust
bean kernels, soy beans and carbon granulate for at least 24
hours.
EXAMPLE 22
A printing paste for printing a polyamide carpet with cut loops was
produced according to the following recipe:
______________________________________ 400 g of a 3% solution of
hydroxypropyl cassia (produced according to Example 1) 450 g water
3 g C.I. Acid Red 275 20 g butyl diglycol 8 g arylalkyl polyglycol
ether 12 g ammonium sulfate 2 g defoaming agent y g makeup 1,000 g
______________________________________
A second printing paste was prepared with a 3% solution of
hydroxypropylized LBG, and otherwise as above. The two color pastes
were adjusted to equal viscosity and printed for comparison on the
given substrate, on a rotary printing machine. The prints were
fixed and finished. The prints obtained clearly showed that the use
of hydroxypropyl cassia according to the invention as thickening
agent in a dye paste gave better printing results than use of the
LBG ether. This is evidenced in a better penetration of the
printing paste into the substrate and a reduced amount of
graying.
EXAMPLE 23
The printing pastes prepared according to Example 22 were adjusted
to the same viscosity of 3,500 mPas on the Brookfield viscometer
RVT (20 rpm, 20.degree. C.).
Both pastes were measured on the Rotovisco II, of the firm of
Haake, and a so-called flow curve was produced by simultaneous
measurement/recording of the pair of values, shearing stress and
shear gradient, for determination of the rheological
properties.
The paste prepared from hydroxypropyl cassia showed "longer,
tackier" flow behavior in comparison to the other.
This also explains the better penetration of the thickening
according to the invention, as observed in Example 22.
EXAMPLE 24
Dye pastes for spaces of polyamide knitted tubes were prepared
according to the following recipe:
______________________________________ x g dyestuff 15 g butyl
diglycol 15 g alkylaryl polyglycol ether 200 g thickening, 3% 12 g
acetic acid, 60% 2 g defoamer y g water 1,000 g
______________________________________
As a comparison thickening there were used:
(1) hydroxyethyl cassia according to the invention (produced
according to Example 2)
(2) hydroxyethyl guar
(3) hydroxyethyl LBG
The following were chosen as dyestuffs for the comparison:
Bottom color:
2.0 g C.I. Acid Blue 264
0.2 g C.I. Acid Gree 41
Print 1:
2.0 g C.I. Acid Black 172
Print 2:
6.0 g C.I. Acid Blue 264
4.0 g C.I. Acid Blue 260
The dye pastes were adjusted to equal viscosity. After padding and
printing, the dyestuffs were fixed at 102.degree. C. for 10 minutes
in saturated steam.
A comparison of the color yield and also of later processability on
parting the knitted tubes showed no difference between the
thickening of hydroxyethyl cassia according to the invention and
the thickening of hydroxyethyl LBG. However, both thickenings were
clearly superior in their printing appearance to the thickening of
hydroxyethyl guar.
EXAMPLE 25
For printing with disperse dyestuffs on polyester woven and knitted
fabrics, three dye pastes were prepared according to the following
recipe:
______________________________________ 20 g C.I. Disperse Red 90 40
g C.I. Disperse Red 54 600 g thickening solution, acidified with
citric acid to pH 5.2 12 g fixing accelerator 1 g defoamer y g
makeup 1,000 g dye paste ______________________________________
The thickening solution of dye paste 1 was prepared at 5% and had
the following composition: 75 parts of depolymerized hydroxyethyl
cassia combined with 25 parts of starch ether.
The thickening solution of dye paste 2 consisted of a combination
of 75 parts of depolymerized guar with 25 parts of starch ether and
had to be applied at 7% in order to have the same viscosity as dye
paste 1.
The thickening solution of dye paste 3 consisted of a combination
of 75 parts of alkoxylated LBG with, again, 25 parts of starch
ether. For adjustment to equal viscosity to dye pastes 1 and 2, an
8% mixture was necessary.
The comparison printings took place on flat film, rotary, and
cylinder printing machines. Fixing of the prints was performed in
superheated steam.
Comparison of the prints showed that, as regards penetration and
evenness, dye paste 1 with its 5% thickening solution gave an
equally good, and in part even better, result on all printing units
than dye pastes 2 and 3, the thickening solutions of which had to
be prepared at 7% and 8% respectively. The prints of dye pastes 1
and 2 were judged to be equally good in depth of color and
brilliance; as opposed to this, the prints with dye paste 3 turned
out somewhat weaker.
It is clear from this example that equally good--and in part even
better--printing results are obtained when hydroxypropyl cassia is
used as the thickening agent, at a far lower mixture concentration,
than with the fuller-bodied thickening agents described in the
Example.
EXAMPLE 26
For dyeing to solid shades of polyamide carpet with cut loops, on a
dyeing unit with dye application roller, two dye liquors were
prepared according to the following recipe:
______________________________________ 5 g C.I. Acid Brown 331 200
g thickening solution 2.5% 5 g alkoxylated fatty acid amide 3 g
acetic acid 60% 1 g defoamer 786 g water 1,000 g dye liquor
______________________________________
The thickening solution of dye liquor 1 was produced with
hydroxyethyl cassia, and of dye liquor 2 with hydroxyethyl LBG.
After finishing of the dyed display goods it could be seen that the
substrate dyed with dye liquor 1 had a deeper-colored and also more
brilliant appearance than the material dyed for comparison with dye
liquor 2.
EXAMPLE 27
A printing paste for printing with cationic dyestuffs on
polyacrylonitrile was prepared according to the following
recipe:
______________________________________ 35 g C.I. Basic Yellow 11 5
g C.I. Basic Blue 1 600 g thickening solution 20 g acetic acid 30%
20 g Luprintan PFD (R) 10 g Glyecin A (R) x g makeup 1,000 g
______________________________________
The thickening solution consisted
______________________________________ in Case A of 60 parts by
weight depolymerized, cationic cassia ether (trimethylammonium
hydroxypropyl cassia chloride) 40 parts by weight British gum in
Case B of 60 parts by weight depolymerized guar 40 parts by weight
British gum in Case C of 60 parts by weight carboxymethyl locust
bean gum 40 parts by weight British gum
______________________________________
The printing pastes were adjusted to equal viscosity and printed on
polyacrylonitrile muslin, then fixed in saturated steam for 30
minutes.
The print according to recipe C was spotty, agglomerates obviously
having arisen between the cationic dyestuff and the anionic
galactomannan ether.
Recipe A gave a far more level and brilliant dye appearance than
Recipe B.
EXAMPLE 28
500 l of finished sizing liquor were prepared in the Turbo-cooker
with 25 kg of hydroxypropyl cassia galactomannan sizing agent
according to Example 5 and 1.0 kg sizing wax. The following warp
material was sized on a drum sizing machine: Nm 10/1
polyacrylonitrile yarn 100%, with 2,400 threads and the weaving
set-up: threads per cm 17/17
Yarn count warp and yarn count filling each 10/1 The liquor
temperature was 80.degree. C. in the sizing trough. The warp yarn
was immersed twice and squeezed out twice. The liquor pickup was
124%. The warp was woven on Jacquard looms to curtains. The
efficiency was about 94%.
EXAMPLE 29
450 l of finished sizing liquor were prepared from 35 kg of
hydroxypropyl cassia galactomannan according to Example 5, with the
addition of 100 g of potassium persulfate and 1.5 kg of sizing
grease.
The following warp material was sized: Nm 64/1 polyester/cotton in
a 50%:50% blend ratio with 5,024 threads in the weaving set-up:
34/25-64/64. A drum sizing machine with 9 drying cylinders was
available as the sizing machine. The liquor temperature was
80.degree. C. The warp yarn was immersed twice in the liquor and
squeezed twice with a squeezing performance of 129%. In the weaving
room, an efficiency of 97% was achieved. Dust fallout was extremely
small, both in the drying area of the sizing machine and in the
weaving room.
EXAMPLE 30
450 l of finished sizing liquor were prepared in a Turbo-cooker
with 35 kg of carboxymethyl cassia galactomannan according to
Example 3, 150 g of potassium persulfate, and 0.5 kg of sizing
grease. The following warp material was sized: Nm 70/1 cotton,
provided for bed-ticking fabric, with 6,580 threads in the weaving
set-up: 47/42-70/70. A drum sizing machine with 9 drying cylinders
and 2 sizing troughs was available as the sizing machine. The
liquor temperature during sizing was 80.degree.-85.degree. C. The
warp yarn was immersed twice in the liquor and twice squeezed out
with a squeezing performance of 134%. In the weaving room, an
efficiency of 97% was achieved.
* * * * *